COLD ROLLED STEEL SHEET OF EXCELLENT DELAYED FRACTURE RESISTANCE AND SUPERHIGH STRENGTH AND METHOD OF MANUFACTURING THE SAME

Abstract: A cold rolled steel sheet of excellent delayed fracture resistance and a superhigh strength substantially consisting of 0.1-0.25 wt.% of carbon (C), not more than 1 wt.% of silicon (Si), 1-2.5 wt.% of manganese (Mn), not more than 0.020 wt.% of phosphorus (P), not more than 0.005 wt.% of sulfur (S), 0.01-0.05 wt.% of soluble aluminum (Sol. Al), 0.0010-0.0050 wt.% of nitrogen (N), and iron and unavoidable impurities for the rest. This cold rolled steel sheet satisfies the relationships: TS≧320x(Ceq)²-155xCeq+102 (1), wherein Ceq = C+(Si/24)+(Mn/6) , and P DF ≧0 (2), wherein R DF = -lnTS+exp(Rr/100+2.95 ; P DF index of delayed fracture resistance; TS tensile strength (kgf/mm²); and Rr a residual strength ratio (%) expressed by (bending-bending-back tensile strength)/(tensile strength)x100 of a steel sheet V-bent at 90° with a radius of 5 mm in the direction which is at right angles to the rolling direction.

Description: FIELD OF THE INVENTION The present invention relates to a method for manufacturing an ultra-high-strength cold-rolled steel sheet excellent in delayed fracture resistance. BACKGROUND OF THE INVENTION For the purpose of reducing the weight of an automobile or ensuring the safety of passengers, cold-rolled steel sheets having such a high tensile strength as to permit achievement of a higher strength and reduction of the weight of various structural members, are widely used as materials for protective components of an automobile such as a bumper reinforcement and a door guard bar. As a cold-rolled steel sheet having such a high tensile strength, ultra-high-strength cold-rolled steel sheets having a tensile strength of over 981 MPa (100 kgf/mm 2 ) are proposed as follows: (1) an ultra-high-strength cold-rolled steel sheet, disclosed in Japanese Patent Provisional Publication No. 61-3,843 published on January 9, 1986, which consists essentially of: carbon (C) from 0.02 to 0.30 wt.%, silicon (Si) from 0.01 to 2.5 wt.%, manganese (Mn) from 0.5 to 2.5 wt.%, and the balance being iron (Fe) and incidental impurities (hereinafter referred to as the "prior art 1"). (2) an ultra-high-strength cold-rolled steel sheet, disclosed in Japanese Patent Provisional Publication No. 61-217,529 published on September 27, 1986, which consists essentially of: carbon (C) from 0.12 to 0.70 wt.%, silicon (Si) from 0.4 to 1.0 wt.%, manganese (Mn) from 0.2 to 2.5 wt.%, soluble aluminum (Sol.Al) from 0.01 to 0.07 wt.%, nitrogen (total N) up to 0.02 wt.%, and the balance being iron (Fe) and incidental impurities (hereinafter referred to as the "prior art 2"). However, the prior arts 1 and 2 described above have the following problems: It is true that the cold-rolled steel sheets of the prior arts 1 and 2 are excellent in workability and have a high tensile strength of over 981 MPa (100 kgf/mm 2 ). An ultra-high-strength cold-rolled steel sheet having a tensile strength of over 981 MPa (100 kgf/mm 2 ) is usually formed through the bending. In the cold-rolled steel sheets of the prior arts 1 and 2, however, when the tensile strength of the steel sheet becomes higher over 981 MPa (100 kgf/mm 2 ), a fracture phenomenon (hereinafter referred to as the "delayed fracture") is suddenly caused by hydrogen penetrating into the interior of the steel sheet under the effect of a corrosion reaction taking place along with the lapse of time at a portion formed by the above-mentioned bending of the cold-rolled steel sheet. Therefore, even with a high tensile strength, a cold-rolled steel sheet susceptible to the delayed fracture, has a fatal defect as a material for protective components of an automobile, for example. US-A-3 573 898 discloses a high-yield-strength steel for low temperature services, consisting essentially of 0.01 to 0.20% C, 0.10 to 0.60% Si, 1.00 to 1.50% Mn, 0.10 to 0.30% Cu, 0.10 to 0.40% Cr, 0.020 to 0.060% Sol Al, 0.008 to 0.020% N and the balance being Fe and unavoidable impurities, said steel having high tensile-strength of more than 491 MPa (50 kgf/mm 2 ), high yield-strength of more than 343 MPa (35 kgf/mm 2 ) excellent low-temperature toughness and good weldability. Under such circumstances, there is a strong demand for the development of a method for manufacturing an ultra-high-strength cold-rolled steel sheet excellent in the property inhibiting the occurrence of delayed fracture (hereinafter referred to as "delayed fracture resistance") and having a high tensile strength of over 981 MPa (100 kgf/mm 2 ), but such a method for manufacturing an ultra-high-strength cold-rolled steel sheet have not as yet been proposed. An object of the present invention is therefore to provide a method for manufacturing an ultra-high-strength cold-rolled steel sheet excellent in delayed fracture resistance and having a high tensile strength of over 981 MPa (100 kgf/mm 2 ). DISCLOSURE OF THE INVENTION In accordance with one of the features of the present invention, there is provided a method for manufacturing an ultra-high-strength cold-rolled steel sheet excellent in delayed fracture resistance, which comprises the steps of: preparing a material consisting of: carbon (C) from 0.1 to 0.25 wt.%, silicon (Si) up to 1 wt.%, manganese (Mn) from 1 to 2.5 wt.%, phosphorus (P) up to 0.020 wt.%, sulfur (S) up to 0.005 wt.%, soluble aluminum (Sol.Al) from 0.01 to 0.05 wt.%, nitrogen (N) from 0.0010 to 0.0050 wt.%, optionally, in addition at least one element selected from the group consisting of: niobium (Nb) from 0.005 to 0.05 wt.%, titanium (Ti) from 0.005 to 0.05 wt.%, and vanadium (V) from 0.01 to 01. wt.% and/or optionally, in addition at least one element selected from the group consisting of: copper (Cu) from 0.1 to 1.0 wt.%, nickel (Ni) from 0.1 to 1.0 wt.%, boron (B) from 0.0005 to 0.0030 wt.%, chromium (Cr) from 0.1 to 1.0 wt.%, and molybdenum (Mo) from 0.1 to 0.5 wt.%, and the balance being iron (Fe) and incidental impurities; subjecting said material to a hot rolling, a pickling and a cold rolling to prepare a cold-rolled steel sheet; and then subjecting said cold-rolled steel sheet thus prepared to a continuous heat treatment which comprises the steps of: subjecting said cold-rolled steel sheet to a soaking treatment at a temperature within a range of from Ac, to 900°C for a period of time within a range of from 30 seconds to 15 minutes, then quenching said cold-rolled steel sheet at a quenching rate of at least 400°C /second from a temperature of at least a lower limit temperature (T Q ) for starting quenching as expressed by the following formula to a temperature of up to 100°C: T Q (°C) = 600 + 800 × C + (20 × Si + 12 × Mo + 13 × Cr) - (30 × Mn + 8 × Cu + 7 × Ni + 5000 × B), and then, tempering said cold-rolled steel sheet at a temperature within a range of from 100 to 300°C for a period of time within a range of from 1 to 15 minutes. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a graph illustrating the relationship between an evaluation of delayed fracture resistance and a delayed fracture resistance index (P DF ) in an ultra-high-strength cold-rolled steel sheet; Fig. 2 is a graph illustrating the effect of a residual strength ratio (Rr) and tensile strength (TS) on a delayed fracture resistance index (P DF ) in an ultra-high-strength cold-rolled steel sheet; Fig. 3 is a graph illustrating the effect of Ceq (= C + (Si/24) + (Mn/6)) on the lower limit value of tensile strength (TS) in an ultra-high-strength cold-rolled steel sheet; Fig. 4 is a graph illustrating the effect of manufacturing conditions on a delayed fracture resistance index (P DF ) in an ultra-high-strength cold-rolled steel sheet; Fig. 5 is a schematic descriptive view illustrating the steps for measuring a residual strength ratio (R r ) in an ultra-high-strength cold-rolled steel sheet; and Fig. 6 is a schematic descriptive view illustrating the steps for preparing a test piece for evaluating delayed fracture resistance in an ultra-high-strength cold-rolled steel sheet. DESCRIPTION OF PREFERRED EMBODIMENTS From the above-mentioned point of view, extensive studies were carried out to develop a method for manufacturing an ultra-high-strength cold-rolled steel sheet excellent in delayed fracture resistance and having a high tensile strength of over 981 MPa (100 kgf/mm 2 ). As a result, the following findings were obtained. For an ultra-high-strength cold-rolled steel sheet having a high tensile strength of over 981 MPa (100 kgf/mm 2 ) susceptible to the delayed fracture after the working, various factors having effects on delayed fracture resistance and the influence thereof were investigated. The investigation revealed that delayed fracture resistance of an ultra-high-strength cold-rolled steel sheet after the working was determined by tensile strength of the cold-rolled steel sheet and the degree of deterioration of the material of the cold-rolled steel sheet caused by the working. More specifically: (1) According as tensile strength of a cold-rolled steel sheet becomes larger, delayed fracture resistance of the cold-rolled steel sheet is deteriorated. (2) According as the degree of deterioration of the material of a cold-rolled steel sheet caused by the working becomes larger, delayed fracture resistance of the cold-rolled steel sheet is deteriorated; and (3) According as the uniformity of the structure of a cold-rolled steel sheet decreases, the degree of deterioration of the material of the cold-rolled steel sheet caused by the working becomes larger. It is therefore possible to obtain an ultra-high-strength cold-rolled steel sheet excellent in delayed fracture resistance even after the working and having a high tensile strength of over 981 MPa (100 kgf/mm 2 ), by increasing the uniformity of the structure of the steel sheet and specifying the degree of deterioration of the material of the steel sheet, which corresponds to tensile strength of the steel sheet. The present invention was made on the basis of the above-mentioned findings. The ultra-high-strength cold-rolled steel sheet prepared according to the present invention excellent in delayed fracture resistance and having a high tensile strength of over 981 MPa (100 kgf/mm 2 ) and the method for manufacturing same, are described below in detail. The reasons of limiting the chemical composition of the cold-rolled steel sheet prepared according to the present invention within the above-mentioned ranges are described below. Carbon is an element having a function of increasing strength of a low-temperature transformation phase (for example, a martensitic structure or a bainitic structure). A carbon content of under 0.1 wt.% cannot however give a desired effect as described above. A carbon content of over 0.25 wt.% results on the other hand in a seriously decreased shock resistance to cause a deteriorated delay fracture resistance of the steel sheet. The carbon content should therefore be limited within a range of from 0.1 to 0.25 wt.%. (2) Silicon (Si): Silicon is an element having a function of increasing ductility and temper-softening resistance of a steel sheet. A silicon content of over 1 wt.% causes however a considerable grain boundary oxidation in the surface portion of the steel sheet so that, upon the application of a stress to the steel sheet, the stress concentrates in the surface portion of the steel sheet, in which the grain boundary oxidation took place, thus resulting in the deterioration of delayed fracture resistance of the steel sheet. The silicon content should therefore be limited to up to 1 wt.%. (3) Manganese (Mn): Manganese is a low-cost element having a function of increasing hardenability of steel and giving a low-temperature transformation phase to steel. A manganese content of under 1 wt.% cannot however give a desired effect as described above. With a manganese content of over 2.5 wt.%, on the other hand, a banded structure caused by the segregation of manganese during the casting grows considerably in steel, deteriorating the uniformity of the structure of steel, and thus causes the deterioration of delayed fracture resistance of the steel sheet. The manganese content should therefore be limited within a range of from 1 to 2.5 wt.%. (4) Phosphorus (P): With a phosphorus content of over 0.020 wt.%, phosphorus segregates along grain boundaries of steel to cause the deterioration of delayed fracture resistance of the steel sheet. The phosphorus content should therefore be limited to up to 0.020 wt.%. (5) Sulfur (S): With a sulfur content of over 0.005 wt.%, a large amount of non-metallic inclusions (MnS) extending in the rolling direction are produced, and this causes the deterioration of delayed fracture resistance of the steel sheet. The sulfur content should therefore be limited to up to 0.005 wt.%. (6) Soluble aluminum (Sol.Al): Soluble aluminum is contained in steel as a residue of aluminum (Al) used as a deoxidizer. However, with a soluble aluminum content of under 0.01 wt.%, silicate inclusions remain in steel, thus causing the deterioration of delayed fracture resistance of the steel sheet. A soluble aluminum content of over 0.05 wt.% increases, on the other hand, surface flaws of the steel sheet to easily cause a delayed fracture of the steel sheet. The soluble aluminum content should therefore be limited within a range of from 0.01 to 0.05 wt.%. (7) Nitrogen (N): With a nitrogen content of under 0.0010 wt.%, there decrease nitrides in steel, leading to a coarser structure of steel, and hence to the deterioration of delayed fracture resistance of the steel sheet. with a nitrogen content of over 0.0050 wt.%, on the other hand, nitrides in steel become coarser, thus resulting in the deterioration of delayed fracture resistance of the steel sheet. The nitrogen content should therefore be limited within a range of from 0.0010 to 0.0050 wt.%. (8) The ultra-high-strength cold-rolled steel sheet of the present invention may further additionally contain, in addition to the above-mentioned chemical composition, at least one element selected from the group consisting of: from 0.005 to 0.05 wt.% niobium (Nb), from 0.005 to 0.05 wt.% titanium (Ti), and from 0.01 to 0.1 wt.% vanadium (V). Niobium, titanium and vanadium have a function of forming carbon nitrides to achieve a finer structure of steel. For any of these elements, however, a content of under the respective lower limits cannot give a desired effect as described above. with a content of over the respective upper limits, on the other hand, the above-mentioned desired effect is saturated, and at the same time, carbon nitrides becoming coarser cause the deterioration of delayed fracture resistance of the steel sheet. The respective contents of niobium, titanium and vanadium should therefore be limited within the above-mentioned ranges. (9) The ultra-high-strength cold-rolled steel sheet of the present invention may further additionally contain, in addition to the above-mentioned chemical compositions, at least one element selected from the group consisting of: from 0.1 to 1.0 wt.% copper (Cu), from 0.1 to 1.0 wt.% nickel (Ni), from 0.0005 to 0.0030 wt.% boron (B), from 0.1 to 1.0 wt.% chromium (Cr) and from 0.1 to 0.5 wt.% molybdenum (Mo). Copper, nickel, boron, chromium and molybdenum have, just as manganese, a function of increasing hardenability of steel. For any of these elements, with a content of under the respective lower limits, however, the desired effect as described above is not available. With a content of over the respective upper limits, on the other hand, the above-mentioned desired effect is saturated. The respective contents of copper, nickel, boron, chromium and molybdenum should therefore be limited within the above-mentioned ranges. Now, the reason of specifying tensile strength (TS) of a cold-rolled steel sheet as expressed by the following formula (1) in terms of Ceq (= C + (Si/24) + (Mn/6)) is described below: TS ≧ 320 × (Ceq) 2 - 155 × Ceq + 102 A high manganese content in steel promotes, as described above, formation of the banded structure in steel caused by the segregation of manganese during the casting, and thus causes the deterioration of delayed fracture resistance of the steel sheet. Formation of such a banded structure caused by the segregation of manganese is characterized in that: (1) formation of the banded structure is accelerated under the effect of coexistence of manganese with carbon (C) and silicon (Si), and (2) formation of the banded structure becomes more remarkable according as the structure of steel becomes composite (i.e., ferritic phase + low-temperature transformation phase). According as the structure of steel becomes more composite, furthermore, tensile strength of the cold-rolled steel sheet decreases. It is therefore necessary to inhibit formation of the banded structure in steel caused by the segregation of manganese, which is accelerated under the effect of coexistence of manganese with carbon and silicon, and to prevent the structure of steel from becoming composite. More specifically, the structure of steel is prevented from becoming composite by means of Ceq (= C + (Si/24) +(Mn/6)) as determined by the contents of carbon, silicon and manganese. Since tensile strength-of the cold-rolled steel sheet decreases, as described above, along with the structure of steel becoming more composite, it is necessary to control the lower limit value of tensile strength of the steel sheet by means of the above-mentioned formula (1) as expressed by Ceq, in order to ensure uniformity of the structure of steel. Now, the delayed fracture resistance index (P DF ) is described in the following paragraphs. In order to obtain a cold-rolled steel sheet excellent in delayed fracture resistance even after the working, as described above, it is important to specify the degree of deterioration of the material of the steel sheet, which corresponds to tensile strength of the steel sheet. Experimental data derived from the research reveals that delayed fracture resistance of a cold-rolled steel sheet is improved when a delayed fracture resistance index (P DF ) of the steel sheet as expressed by the following formula (2) takes a value of at least zero: P DF = - ℓnTS + exp[Rr/100] + 2.95 where, TS : tensile strength (kgf/mm 2 ), Rr : residual strength ratio (%) of a steel sheet as expressed by (bending/stretching tensile strength) ÷ (tensile strength) × 100 , when the steel sheet has been subjected to a 90° V-bending with a radius of 5 mm in a direction at right angles to the rolling direction. The first term of the above-mentioned formula (2) (i.e., "-ℓnTS") represents the effect of tensile strength (TS) of the cold-rolled steel sheet on delayed fracture resistance of the steel sheet. A higher tensile strength (TS) of the cold-rolled steel sheet leads to a smaller P DF thereof. The second term of the above-mentioned formula (2) (i.e., "exp[Rr/100]") represents the effect of the degree of deterioration of the material of the cold-rolled steel sheet caused by the working on delayed fracture resistance of the steel sheet. Deterioration of the material of the cold-rolled steel sheet caused by the working reduces the P DF of the steel sheet. The degree of deterioration of the material of the cold-rolled steel sheet caused by the working represents the degree of deterioration of the material of the steel sheet caused by the bending mainly used for forming an ultra-high-strength cold-rolled steel sheet. In the present invention, the degree of deterioration of the material of the steel sheet is represented by, as an index, a residual strength ratio (R r ) of a steel sheet which has been subjected to a 90° V-bending with a radius of 5 mm in a direction at right angles to the rolling direction. The direction at right angles to the rolling direction is selected because the material quality of an ultra-high-strength is poorer in the direction at right angles to the rolling direction than in a direction in parallel with the rolling direction, and evaluation is stricter in this direction. A 90° V-bending is applied with a radius of 5 mm because this manner of working is a bending method most commonly used for an ultra-high-strength cold-rolled steel sheet. Steps for measuring the residual strength ratio (R r ) of a cold-rolled steel sheet is illustrated in Fig. 5. As shown in Fig. 5, the above-mentioned measuring steps comprise: subjecting a portion "a" of a test piece 1 cut out from a cold-rolled steel sheet to a 90° V-bending with a radius of 5 mm in a direction at right angles to the rolling direction; then subjecting both sides "b" of the portion "a" of the test piece 1 to a bending with a radius of 6 mm to form a grip on each of the both end portions of the test piece 1; and then grasping the grips by means of a tensile testor to draw the test piece 1 in directions as indicated by "P" so as to determine a fracture stress at the moment of fracture of the test piece 1 at the portion "a". The thus determined fracture stress is referred to as the bending/stretching tensile strength, and the value calculated in accordance with a formula " (bending/stretch ing tensile strength)÷ (tensile strength before bending) × 100 ", is adopted as the residual strength ratio (R r ) (%) of the cold-rolled steel sheet. The third term of the above-mentioned formula (2) (i.e., "+2.95") represents the correction for making the critical value of P DF zero. Now, the reasons of limiting the manufacturing method of the present invention within the above-mentioned ranges are described below. As described above in the findings, delayed fracture resistance of a cold-rolled steel sheet can be improved by increasing uniformity of the structure of the steel sheet and specifying the degree of deterioration of the material of the steel sheet, which corresponds to tensile strength of the steel sheet. In the manufacturing method of the present invention, therefore, it is important to make up for the deterioration of delayed fracture resistance of the cold-rolled steel sheet caused according as tensile strength of the steel sheet becomes larger, by uniforming the structure of the steel sheet to inhibit deterioration of the material of the steel sheet caused by the bending. For this purpose, a material having a specific chemical composition is first hot-rolled and cold-rolled by the conventional methods to prepare a cold-rolled steel sheet, and then, the cold-rolled steel sheet thus prepared is subjected, in a continuous annealing, to a soaking treatment at a temperature within a range of from Ac 3 to 900°C for a period of time within a range of from 30 seconds to 15 minutes. when a soaking treatment is applied at a temperature of under Ac 3 , an as-rolled structure remains in the cold-rolled steel sheet to deteriorate uniformity of the structure of the steel sheet. Application of the soaking treatment to the cold-rolled steel sheet at a temperature of over 900°C, on the other hand, gives rise to various operational problems, and, furthermore, the structure of steel becomes coarser to cause the deterioration of delayed fracture resistance of the steel sheet. Application of the soaking treatment to the cold-rolled steel sheet for a period of time of under 30 seconds makes it impossible to obtain a stable austenitic phase. When the soaking treatment is applied to the cold-rolled steel sheet for a period of time of over 15 minutes, on the other hand, the effect reaches saturation thereof. The conditions for the soaking treatment should therefore be limited within the ranges described above. Then, the cold-rolled steel sheet, which has been subjected to the above-mentioned soaking treatment to control the strength level thereof,preferably is then slowly coole The slow cooling rate should appropriately be within a range of from 1 to 30°C/second to minimize variations in the material quality in the width direction and the longitudinal direction of the steel sheet. Thereafter, the cold-rolled steel sheet is quenched. When the quenching starting temperature is low, the volume ratio of the precipitated ferritic phase increases, thus causing the deterioration of uniformity of the structure of the steel sheet. The quenching starting temperature should therefore be limited to at least a lower limit temperature (T Q ) for starting quenching as expressed by the following formula: T Q (°C) = 600 + 800 × C + (20 × Si + 12 × Mo + 13 × Cr) - (30 × Mn + 8 × Cu + 7 × Ni + 5000 × B) In the above-mentioned formula, the elements such as C and Si are represented in wt.% a as unit. In this formula, furthermore, the elements Si, Mo and Cr, which have a function of increasing the Ar 3 transformation point, act to increase the T Q because they promote precipitation of the ferritic phase. The elements Mn, Cu, Ni and B, which have a function of decreasing the Ar 3 transformation point, act to reduce the T Q because they inhibit precipitation of the ferritic phase. The element C, which has a function of reducing the Ar 3 transformation point, just as Mn, Cu, Ni and B, has an effect on the T Q , unlike Mn, Cu, Ni and B. More specifically, even in a structure of steel having a ferritic phase of the same volume ratio, a higher C content leads to an increased difference in hardness between the low-temperature transformation phase and the ferritic phase, so that, upon the working, strain concentrates on the interface, resulting in a considerable deterioration of the material of the steel sheet. With a higher C content, therefore, it is necessary to inhibit precipitation of the ferritic phase. Subsequently, the cold-rolled steel sheet is quenched at a quenching rate of at least 400°C/second from a temperature of at least the above-mentioned lower limit temperature (T Q ) for starting quenching to a temperature of up to 100°C, to obtain a low-temperature transformation phase. When quenching is conducted at a cooling rate of under 400°C/second, or to a temperature of over 100°C, it is necessary to increase the contents of elements required for obtaining a desired high strength. This results in a higher manufacturing cost, and in addition, the mixed existence of the martensitic structure and the bainitic structure causes the deterioration of uniformity of the structure of the steel sheet. The quenching rate and the quenching stoppage temperature should therefore be limited within the above-mentioned ranges. Then, the cold-rolled steel sheet is subjected to a tempering treatment, since an as-quenched martensitic phase of the steel sheet is brittle and thermally unstable. The tempering treatment is applied at a temperature within a range of from 100 to 300°C for a period of time within a range of from 1 to 15 minutes. A tempering treatment at a temperature of under 100°C results in an insufficient tempering of the martensitic phase. A tempering treatment at a temperature of over 300°C causes, on the other hand, the precipitation of carbides on the crystal grain boudaries, and hence a serious deterioration of the material of the steel sheet caused by the working. A tempering treatment for a period of time of under one minute results in an insufficient tempering of the martensitic phase. when a tempering treatment is applied for a period of time of over 15 minutes, the tempering effect is saturated. Now, the ultra-high-strength cold-rolled steel sheet of the present invention excellent indelayed fracture resistance and the method for manufacturing same, are described further in detail by means of examples while comparing with examples for comparison. EXAMPLES Steels "A" to "Z" having chemical compositions within the scope of the present invention as shown in Table 1, and steels "a" to "j" having chemical compositions outside the scope of the present invention as shown also in Table 1, were tapped from a converter, and then, were continuously cast into respective slabs. The resultant slabs were then hot-rolled under conditions including a heating temperature of 1,200°C, a finishing temperature of 820°C and a coiling temperature of 600 °C, to prepare hot-rolled steel sheets having a thickness of 3 mm. Then, the thus prepared hot-rolled steel sheets were pickled and cold-rolled to prepare cold-rolled steel sheets having a thickness of 1.4 mm. The thus prepared cold-rolled steel sheets were then subjected to a heat treatment in a combination-type continuous annealing line including a water-quenching apparatus and a roll-cooling apparatus under conditions as shown in Tables 2 and 4. The water quenching was applied at a cooling rate of about 1,000°C/second, and the rolling quenching was applied at a cooling rate of about 200°C/second. Thus, there were prepared samples of the cold-rolled steel sheets of the present invention, having chemical compositions within the scope of the present invention and subjected to heat treatments within the scope of the present invention (hereinafter referred to as the "samples of the invention") Nos. 1 to 3, 6 to 9, 11, 13, 15, 17 to 24, 26, 28, 29, 32 to 38, 40, 42, 43, 48, 50, 52 to 54, 56, 57, 59 to 64, 66, 68, 71, 72, 91, 92, 94 and 95, and, samples of the cold-rolled steel sheets having chemical compositions outside the scope of the present invention, and samples of the cold-rolled steel sheets, which, having chemical compositions within the scope of the present invention, were subjected to heat treatments outside the scope of the present invention (hereinafter referred to as the "samples for comparison") Nos. 4, 5, 10, 12, 14, 16, 25, 27, 30, 31, 39, 41, 44 to 47, 49, 51, 55, 58, 65, 67, 69, 70, 73 to 85, 93 and 96 to 98 were prepared. For each of the above-mentioned samples of the invention and samples for comparison, tensile strength (TS), a residual strength ratio (R r ) a delayed fracture resistance index (P DF ) and delayed fracture resistance were investigated. The results are shown in Tables 3 and 4. Sample No. Kind of Steel Ceq Soaking temperature (°C) Lower limit temperature for quench. start (°C) Quench. start temperature (°C) Tempering temperature (°C) Tempering time (sec.) Lower limit of tensile strength(MPa(kgf/mm 2 )) 1 A 0.40 850 654 730 200 600 893 (91) 2 A 0.40 850 654 720 200 600 893 (91) 3 A 0.40 890 654 780 150 300 893 (91) 4 A 0.40 * 802 654 660 240 180 893 (91) 5 B 0.43 850 737 * 720 300 300 932 (95) 6 B 0.43 820 737 740 270 900 932 (95) 7 C 0.42 850 683 770 100 100 912 (93) 8 C 0.42 * 800 683 750 220 800 912 (93) 9 C 0.42 850 683 710 220 700 912 (93) 10 D 0.63 800 732 * 700 120 520 1285 (131) 11 D 0.63 820 732 780 180 300 1285 (131) 12 D 0.63 820 732 750 * 350 450 1285 (131) 13 D 0.63 850 732 740 260 120 1285 (131) 14 D 0.63 850 732 * 680 260 120 1285 (131) 15 E 0.55 840 732 750 260 80 1118 (114) 16 E 0.55 840 732 * 700 200 600 1118 (114) 17 E 0.55 840 732 740 200 510 1118 (114) 18 F 0.44 850 635 760 200 540 1942 (96) 19 G 0.34 850 716 770 110 700 844 (86) 20 G 0.34 850 716 720 250 220 844 (86) 21 H 0.45 820 753 770 100 600 952 (97) 22 H 0.45 820 753 * 750 290 600 952 (97) 23 I 0.43 850 689 760 180 60 932 (95) 24 I 0.43 850 689 700 240 900 932 (95) Ceq = C + Si/24 +Mn/6 Lower limit of tensile strength = 320 × (Ceq) 2 - 155 × Ceq + 102 Mark "*" shows outside the scope of the present invention. Sample No. Kind of Steel Ceq Soaking temperature (°C) Lower limit temperature for quench. start (°C) Quench. start temperature (°C) Tempering temperature (°C) Tempering time (sec.) Lower limit of tensile strength(MPa (kgf/mm 2 )) 25 J 0.51 830 706 * 700 * 400 800 1040 (106) 26 J 0.51 830 706 750 180 800 1040 (106) 27 J 0.51 830 706 * 680 200 800 1040 (106) 28 J 0.51 830 706 740 250 800 1040 (106) 29 J 0.51 830 706 745 250 500 1040 (106) 30 J 0.51 830 706 * 610 250 500 1040 (106) 31 K 0.57 * 800 639 720 200 500 1158 (118) 32 K 0.57 840 639 750 220 400 1158 (118) 33 K 0.57 840 639 720 130 400 1158 (118) 34 L 0.40 830 678 730 200 900 893 (91) 35 L 0.40 850 678 710 260 500 893 (91) 36 L 0.40 850 678 * 660 200 800 893 (91) 37 M 0.33 840 692 730 130 700 844 (86) 38 M 0.33 840 692 710 130 700 844 (86) 39 M 0.33 840 692 * 680 130 700 844 (86) 40 N 0.43 840 659 740 260 100 932 (95) 41 0 0.61 840 707 750 * 360 600 1246 (127) 42 0 0.61 840 707 750 270 900 1246 (127) 43 0 0.61 840 707 750 120 900 1246 (127) 44 0 0.61 790 707 * 620 260 410 1246 (127) 45 P 0.44 880 784 * 720 200 500 942 (96)- 46 P 0.44 880 784 * 760 200 500 942 (96) 47 P 0.44 880 784 800 * 320 500 942 (96) 48 Q 0.44 870 624 770 150 800 942 (96) Ceq = C+Si/24 +Mn/6 Lower limit of tensile strength = 320 × (Ceq) 2 - 155 × Ceq +102 Mark "*" shows outside the scope of the present invention. Sample No. Kind of Steel Ceq Soaking temperature (°C) Lower limit temperature for quench. start (°C) Quench. start temperature (°C) Tempering temperature (°C) Tempering time (sec.) Lower limit of tensile strength (MPa (kgf/mm 2 )) 49 R 0.47 840 762 * 700 180 200 981 (100) 50 R 0.47 840 762 770 260 300 981 (100) 51 R 0.47 840 762 780 * 310 400 981 (100) 52 R 0.47 870 762 770 290 750 981 (100) 53 S 0.29 850 648 740 200 100 824 (84) 54 S 0.29 890 648 770 100 550 824 (84) 55 S 0.29 * 820 648 690 200 100 824 (84) 56 T 0.38 840 651 720 250 500 873 (89) 57 U 0.40 820 755 * 710 260 700 893 (91) 58 U 0.40 840 755 770 * 400 800 893 (91) 59 U 0.40 840 755 770 230 150 893 (91) 60 V 0.35 820 684 770 100 500 853 (87) 61 V 0.35 850 684 750 220 700 853 (87) 62 W 0.39 850 731 760 * 450 500 883 (90) 63 W 0.39 850 731 760 260 700 883 (90) 64 X 0.46 830 684 760 180 800 961 (98) 65 X 0.46 * 790 684 740 220 300 961 (98) 66 X 0.46 850 684 710 200 300 961 (98) 67 X 0.46 * 800 684 * 670 200 300 961 (98) 68 Y 0.69 860 731 800 230 420 1442 (147) 69 Y 0.69 860 731 * 728 230 420 1442 (147) 70 Y 0.69 820 731 * 720 270 260 1442 (147) 71 Z 0.66 840 722 790 240 300 1364 (139) 72 Z 0.66 840 722 760 200 180 1364 (139) Ceq= C+Si/24 +Mn/6 Lower limit of tensile strength = 320 × (Ceq) 2 - 155 × Ceq +102 Mark "*" shows outside the scope of the present invention. Sample No. Kind of Steel Ceq Soaking temperature (°C) Lower limit temperature for quench. start (°C) Quench. start temperature (°C) Tempering temperature (°C) Tempering time (sec.) Lower limit of tensile strength(MPa (kgf/mm 2 )) 73 Z 0.66 840 722 * 700 200 180 1364 (139) 74 Z 0.66 870 722 * 720 180 220 1364 (139) 75 a 0.63 830 693 760 120 500 1285 (131) 76 b 0.58 800 625 730 200 900 1177 (120) 77 c 0.51 850 666 750 270 100 1040 (106) 78 d 0.45 850 686 770 100 400 952 (97) 79 e 0.41 820 741 750 230 800 903 (92) 80 e 0.41 820 741 * 700 200 600 903 (92) 81 f 0.52 830 767 770 250 100 1059 (108) 82 g 0.43 860 644 770 180 500 932 (95) 83 h 0.55 820 680 740 200 200 1118 (114) 84 i 0.48 840 699 760 110 700 991 (101) 85 j 0.51 850 651 730 230 100 1040 (106) Ceq= C+Si/24 +Mn/6 Lower limit of tensile strength = 320 × (Ceq) 2 - 155 × Ceq +102 Mark "*" shows outside the scope of the present invention. Sample No. Kind of Steel Tensile strength (MPa (kgf/mm 2 )) Residual strength ratio (%) P DF Delayed fracture resistance evaluation (points) Remarks 1 A 1109 (113) 95 0.808 5 Sample of the invention 2 A 1001 (102) 72 0.379 4 Sample of the invention 3 A 1265 (129) 73 0.165 4 Sample of the invention 4 A * 804 (82) 33 -0.066 0 Sample for comparison 5 B 1256 (128) 60 -0.080 0 Sample for comparison 6 B 1373 (140) 81 0.256 4 Sample of the invention 7 C 1403 (143) 95 0.573 5 Sample of the invention 8 C 1197 (122) 63 0.024 3 Sample of the invention 9 C 1010 (103) 96 0.927 5 Sample of the invention 10 D 1530 (156) 70 -0.086 0 Sample for comparison 11 D 1678 (171) 93 0.343 5 Sample of the invention 12 D *1226(125) 40 -0.386 0 Sample for comparison 13 D 1393 (142) 85 0.334 5 Sample of the invention 14 D *1128(115) 42 -0.273 0 Sample for comparison 15 E 1658 (169) 82 0.091 3 Sample of the invention 16 E 1373 (140) 68 -0.018 0 Sample for comparison 17 E 1481 (151) 79 0.136 4 Sample of the invention 18 F 1099 (112) 100 0.950 5 Sample of the invention 19 G 1472 (150) 95 0.525 5 Sample of the invention 20 G 903 (92) 90 0.888 5 Sample of the invention 21 H 1746 (178) 85 0.108 3 Sample of the invention 22 H 1452 (148) 74 0.049 3 Sample of the invention 23 I 1422 (145) 96 0.585 5 Sample of the invention 24 1 1069 (109) 61 0.099 4 Sample of the invention Mark "*" shows outside the scope of the present invention. Sample No. Kind of Steel Tensile strength (MPa (kgf/mm 2 )) Residual strength ratio (%) P DF Delayed fracture resistance evaluation (points) Remarks 25 J 1128 (115) 53 -0.096 0 Sample for comparison 26 J 1599 (163) 82 0.127 5 Sample of the invention 27 J 1207 (123) 52 -0.180 0 Sample for comparison 28 J 1275 (130) 82 0.353 5 Sample of the invention 29 J 1393 (142) 95 0.580 5 Sample of the invention 30 J *853(87) 35 -0.097 0 Sample for comparison 31 K *1050(107) 30 -0.373 0 Sample for comparison 32 K 1187 (121) 96 0.766 5 Sample of the invention 33 K 1373 (140) 100 0.727 5 Sample of the invention 34 L 1324 (135) 91 0.529 5 Sample of the invention 35 L 1226 (125) 93 0.656 5 Sample of the invention 36 L 1158 (118) 67 0.134 5 Sample of the invention 37 M 1265 (129) 75 0.207 4 Sample of the invention 38 M 1138 (116) 71 0.230 3 Sample of the invention 39 M 1010 (103) 49 -0.052 0 Sample for comparison 40 N 1236 (126) 82 0.384 5 Sample of the invention 41 0 1305 (133) 61 -0.100 0 Sample for comparison 42 O 1472 (150) 78 0.121 4 Sample of the invention 43 O 1628 (166) 90 0.298 5 Sample of the invention 44 O *961(98) 36 -0.202 0 Sample for comparison 45 P 1589 (162) 53 -0.439 0 Sample for comparison 46 P 1746 (178) 80 -0.006 0 Sample for comparison 47 P 1697 (173) 67 -0.249 0 Sample for comparison 48 Q 1177 (120) 91 0.647 5 Sample of the invention Mark "*" shows outside the scope of the present invention. Sample No. Kind of Steel Tensile strength (MPa (kgf/mm 2 )) Residual strength ratio (%) P DF Delayed fracture resistance evaluation (points) Remarks 49 R 1422 (145) 42 -0.505 0 Sample for comparison 50 R 1668 (170) 92 0.323 4 Sample of the invention 51 R 1472 (150) 56 -0.310 0 Sample for comparison 52 R 1030 (105) 75 0.413 4 Sample of the invention 53 S 1030 (105) 96 0.908 5 Sample of the invention 54 S 1079 (110) 75 0.367 5 Sample of the invention 55 S *814(83) 29 -0.132 0 Sample for comparison 56 T 1030 (105) 83 0.589 5 Sample of the invention 57 U 1324 (135) 69 0.038 3 Sample of the invention 58 U 1334 (136) 50 -0.314 0 Sample for comparison 59 U 1550 (158) 96 0.499 5 Sample of the invention 60 V 1373 (140) 87 0.395 4 Sample of the invention 61 V 1177 (120) 93 0.697 5 Sample of the invention 62 W 1177 (120) 62 0.021 3 Sample of the invention 63 W 1393 (142) 98 0.659 5 Sample of the invention 64 X 1226 (125) 93 0.656 5 Sample of the invention 65 X 1118 (114) 42 -0.264 0 Sample for comparison 66 X 1373 (140) 96 0.620 5 Sample of the invention 67 X *932(95) 46 -0.020 0 Sample for comparison 68 Y 1687 (172) 90 0.262 5 Sample of the invention 69 Y *1403(143) 62 -0.154 0 Sample for comparison 70 Y *1265(129) 60 -0.088 0 Sample for comparison 71 Z 1599 (163) 85 0.196 4 Sample of the invention 72 Z 1422 (145) 76 0.112 4 Sample of the invention Mark "*" shows outside the scope of the present invention. Sample No. Kind of Steel Tensile strength (MPa (kgf/mm 2 )) Residual strength ratio (%) P DF Delayed fracture resistance evaluation (points) Remarks 73 Z *1020(104) 40 -0.203 0 Sample for comparison 74 Z *1324(135) 62 -0.096 0 Sample for comparison 75 a 1668 (170) 60 -0.364 0 Sample for comparison 76 b 1334 (136) 97 0.675 0 Sample for comparison 77 c 1275 (130) 88 0.493 1 Sample for comparison 78 d 1403 (143) 100 0.705 0 Sample for comparison 79 e 1570 (160) 100 0.593 0 Sample for comparison 80 e 1275 (130) 52 -0.236 0 Sample for comparison 81 f 1766 (180) 100 0.475 0 Sample for comparison 82 g 1158 (118) 100 0.898 1 Sample for comparison 83 h 1481 (151) 95 0.518 0 Sample for comparison 84 i 1521 (155) 100 0.625 0 Sample for comparison 85 j 1373 (140) 90 0.468 0 Sample for comparison Mark "*" shows outside the scope of the present invention. The above-mentioned residual strength ratio (R r ) of each of the samples of the invention and the samples for comparison was determined in accordance with the method described with reference to Fig. 5. The above-mentioned delayed fracture resistance of each of the samples of the invention and the samples for comparison was evaluated in accordance with the following evaluation method. More specifically, as shown in Fig. 6, a strip-shaped test piece 1 having dimensions of a thickness of 1.4 mm, a width (c) of 30 mm and a length (d) of 100 mm, and having grinding-treated edge faces, was cut out from each of the samples of the invention and the samples for comparison. Then, a hole 2 was pierced in each of both end portions of the strip-shaped test piece 1. A center portion of the test piece 1 was then subjected to a bending with a radius of 5 mm. Then, a bolt 4 made of stainless steel was inserted into the above-mentioned two holes 2 through two washers 3 made of a tetrafluoroethylene resin, which washers inhibited formation of a local cell caused by the contact between different kinds of metal, to tighten the both end portions facing to each other of the test piece 1 by means of the bolt 4 until the distance (e) between the both ends of the test piece 1 became 10 mm, so as to apply stress to the bent portion of the test piece 1. The strip-shaped test piece 1 of each of the samples of the invention and the samples for comparison thus applied with stress was immersed into 0.1 N hydrochloric acid to measure the time required before the occurrence of fractures in the bent portion of the test piece 1. Delayed fracture resistance of each of the samples of the invention and the samples for comparison was evaluated in the above-mentioned measurement by giving an evaluation of delayed fracture resistance of 0 point to the occurrence of fractures in the bent portion within 24 hours, 1 point to the occurrence of fractures within 100 hours, 2 points to the occurrence of fractures within 200 hours, 3 points to the occurrence of fractures within 300 hours, 4 points to the occurrence of fractures within 400 hours (400 hours not included), and 5 points to non-occurrence of fractures upon the lapse of 400 hours. Because the reduction in thickness of the test piece 1 and the production of local corrosion pits were serious after the lapse of 400 hours, the measurement was discontinued upon the lapse of 400 hours. The above-mentioned test results of the residual strength ratio and the delayed fracture resistance are described further in detail with reference to Figs. 1 to 4. Fig. 1 is a graph illustrating the relationship between an evaluation of delayed fracture resistance and a delayed fracture resistance index (P DF ) in an ultra-high-strength cold-rolled steel sheet (i.e., each of the samples of the invention and the samples for comparison). In Fig. 1, the mark "○ " represents a sample comprising any one of steels "A" to "Z" having the chemical compositions within the scope of the present invention, which are free of niobium (Nb), titanium (Ti) and vanadium (V), and the mark "" presents a sample comprising any one of steels "A" to "Z" having the chemical compositions within the scope of the present invention, which contain at least one of niobium, titanium and vanadium. The mark "○ " and the mark "" represent not only the sample of the invention but also the sample for comparison. The mark "▴" represents the sample for comparison comprising any one of steel "a" to "j" having the chemical compositions outside the scope of the present invention. As is clear from Fig. 1, all of the samples of the invention having a P DF (delayed fracture resistance index) of at least 0 show an evaluation of delayed fracture resistance of at least 3 points, and therefore, represent an excellent delayed fracture resistance. All of the samples for comparison show in contrast an evaluation of delayed fracture resistance of up to 1 point even with a P DF of at least 0, and therefore, represent a poor delayed fracture resistance. Fig. 2 is a graph illustrating the effect of a residual strength ratio (R r ) and tensile strength (TS) on a delayed fracture resistance index (P DF ) in an ultra-high-strength cold-rolled steel sheet (i.e., each of the samples of the invention and the samples for comparison). In Fig. 2, the mark "○" represents the sample of the invention having a P DF of at least 0, and the mark "" represents the sample for comparison having a P DF of under 0. As is clear from Fig. 2, all of the samples of the invention having a P DF of at least 0 show a residual strength ratio (R r ) more excellent than that of the samples for comparison relative to the same tensile strength (TS). More specifically, the samples of the invention having a P DF of at least 0 show a residual strength ratio of at least 60%, and the samples of the invention having a high tensile strength of at least1373 MPa (140 kgf/mm 2 )) show a high residual strength ratio of at least 70%. This suggests that the samples of the invention have a high tensile strength as well as an excellent delayed fracture resistance. Fig. 3 is a graph illustrating the effect of Ceq (= C + (Si/24) + (Mn/6)) on the lower limit value of tensile strength (TS) in an ultra-high-strength cold-rolled steel sheet (i.e., each of the samples of the invention and the samples for comparison). In Fig. 3, the mark "○" represents the sample of the invention having a P DF (delayed fracture resistance index) of at least 0, the mark "" represents the sample for comparison having a P DF of under 0, and the curve represents TS (tensile strength) = 320 × (Ceq) 2 - 155 × Ceq + 102. As is evident from Fig. 3, all of the samples of the invention have a high P DF of at least 0 and a high TS of at least 320 × (Ceq) 2 - 155 × Ceq + 102. Some samples for comparison, in contrast, while having a high TS of at least 320 × (Ceq) 2 - 155 × Ceq + 102, have a low P DF of under 0, and the remaining samples for comparison have a low TS of under 320 × (Ceq) 2 - 155 × Ceq + 102 and a low P DF of under 0. More specifically, it is possible, in the samples of the invention, to inhibit formation of the banded structure in steel caused by the segregation of manganese under the effect of the coexistence of manganese with carbon and silicon, and it is also possible to prevent the structure of steel from becoming composite, by using a value of Ceq (= C + (Si/24) + (Mn/6)) as determined by the contents of carbon, silicon and manganese, and controlling the lower limit value of tensile strength (TS) of the cold-rolled steel sheet in response to the value of Ceq. Fig. 4 is a graph illustrating the effect of manufacturing conditions on the delayed fracture resistance index (P DF ) in an ultra-high-strength cold-rolled steel sheet (i.e., each of the samples of the invention and the samples for comparison). In Fig. 4, the mark "○" represents the sample of the invention, the soaking temperature and the tempering temperature of which are within the scope of the present invention as shown in Table 2, the mark "" represents the sample for comparison, the soaking temperature and/or the tempering temperature of which are outside the scope of the present invention also as shown in Table 2, and the mark "▴" represents the sample of the invention or the smple for comparison as shown in Table 4. As is clear from Fig. 4, in order that the P DF (delayed fracture resistance index) is at least 0, it is necessary to limit the quenching start temperature to at least the lower limit temperature (T Q ) for starting quenching, in addition to the control of the soaking temperature and the tempering temperature. According to the present invention, as described above in detail, it is possible to provide a method for manufacturing an ultra-high-strength cold-rolled steel sheet excellent in delayed fracture resistance and having a high tensile strength of over 100 kgf/mm 2 , thus providing many industrially useful effects.

Claims: A method for manufacturing an ultra-high-strength cold-rolled steel sheet excellent in delayed fracture resistance, which comprises the steps of: preparing a material consisting of: carbon (C) from 0.1 to 0.25 wt.%, silicon (Si) up to 1 wt.%, manganese (Mn) from 1 to 2.5 wt.%, phosphorus (P) up to 0.020 wt.%, sulfur (S) up to 0.005 wt.%, soluble aluminum (Sol.Al) from 0.01 to 0.05 wt.%, nitrogen (N) from 0.0010 to 0.0050 wt.%, optionally, in addition at least one element selected from the group consisting of: niobium (Nb) from 0.005 to 0.05 wt.%, titanium (Ti) from 0.005 to 0.05 wt.%, and vanadium (V) from 0.01 to 0.1 wt.%, and/or optionally, in addition at least one element selected from the group consisting of: copper (Cu) from 0.1 to 1.0 wt.%, nickel (Ni) from 0.1 to 1.0 wt.%, boron (B) from 0.0005 to 0.0030 wt.%, chromium (Cr) from 0.1 to 1.0 wt.%, and molybdenum (Mo) from 0.1 to 0.5 wt.%, and the balance being iron (Fe) and incidental impurities; then subjecting said material to a hot rolling, a pickling and a cold rolling to prepare a cold-rolled steel sheet; and then subjecting said cold-rolled steel sheet thus prepared to a continuous heat treatment which comprises the steps of: subjecting said cold-rolled steel sheet to a soaking treatment at a temperature within a range of from Ac 3 to 900°C for a period of time within a range of from 30 seconds to 15 minutes, then quenching said cold-rolled steel sheet at a quenching rate of at least 400°C/second from a temperature of at least a lower limit temperature (T Q ) for starting quenching as expressed by the following formula to a temperature of up to 100°C: T Q (°C) = 600 + 800 × C + (20 × Si + 12 × Mo + 13 × Cr) - (30 × Mn + 8 × Cu + 7 × Ni + 5000 × B), and then, tempering said cold-rolled steel sheet at a temperature within a range of from 100 to 300°C for a period of time within a range of from 1 to 15 minutes. A method as claimed in claim 1, wherein: said material further additionally contains at least one element selected from the group consisting of: niobium (Nb) from 0.005 to 0.05 wt.%, titanium (Ti) from 0.005 to 0.05 wt.%, and vanadium (V) from 0.01 to 0.1 wt.%. A method as claimed in claim 1 or 2 , wherein: said material further additionally contains at least one element selected from the group consisting of: copper (Cu) from 0.1 to 1.0 wt.%, nickel (Ni) from 0.1 to 1.0 wt.%, boron (B) from 0.0005 to 0.0030 wt.%, chromium (Cr) from 0.1 to 1.0 wt.%, and molybdenum (Mo) from 0.1 to 0.5 wt.%

Inventors: HOSOYA YOSHIHIRO, KANETOH SHUZI, NAGATAKI YASUNOBU, OKITA TOMOYOSHI, TAKADA YASUYUKI, TSUYAMA SEISHI, HOSOYA, YOSHIHIRO, KANETOH, SHUZI, NAGATAKI, YASUNOBU, OKITA, TOMOYOSHI, TAKADA, YASUYUKI, TSUYAMA, SEISHI
Applicants: NIPPON KOKAN KK, NKK CORPORATION
Application year: 1994
Main classification: C22C38
IPC codes: C22C38